Catalyst composition, method of polymerization, and polymer therefrom

ABSTRACT

Catalyst compositions and methods, useful in polymerization processes, utilizing at least two metal compounds are disclosed. At least one of the metal compounds is a Group 15 containing metal compound and the other metal compound is preferably a bulky ligand metallocene-type catalyst. The invention also discloses a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.

STATEMENT OF RELATED APPLICATIONS

[0001] The present application is a Continuation Application of U.S.Ser. No. 09/865,067 filed May 24, 2001, which is a DivisionalApplication of, and claims priority to Ser. No. 09/425,387 filed Oct.22, 1999, now issued as U.S. Pat. No. 6,274,684.

FIELD OF THE INVENTION

[0002] The present invention relates to a catalyst compositioncomprising at least two metal compounds useful in olefin polymerizationprocesses to produce polyolefins. Preferably, at least one of the metalcompounds is a Group 15 containing metal compound. More preferably, theother metal compound is a bulky ligand metallocene-type catalyst. Thepresent invention also relates to a new polyolefin, generallypolyethylene, particularly a multimodal polymer and more specifically, abimodal polymer, and its use in various end-use applications such asfilm, molding and pipe.

BACKGROUND OF THE INVENTION

[0003] Polyethylenes with a higher density and higher molecular weightare valued in film applications requiring high stiffness, good toughnessand high throughput. Such resins are also valued in pipe applicationsrequiring stiffness, toughness and long-term durability, andparticularly resistance to environmental stress cracking.

[0004] Typical metallocene polymerization catalysts (i.e. thosecontaining a transition metal bound, for example, to at least onecyclopentadienyl, indenyl or fluorenyl group) have recently been used toproduce resins having desirable product properties. While these resinshave excellent toughness properties, particularly dart impactproperties, they, like other metallocene catalyzed polyethylenes, can bedifficult to process, for example, on older extrusion equipment. One ofthe means used to improve the processing of such metallocene catalyzedpolyethylenes is to blend them with another polyethylene. While the twopolymer blend tends to be more processable, it is expensive and adds acumbersome blending step to the manufacturing/fabrication process.

[0005] Higher molecular weight confers desirable mechanical propertiesand stable bubble formation onto polyethylene polymers. However, it alsoinhibits extrusion processing by increasing backpressure in extruders,promotes melt fracture defects in the inflating bubble and potentially,promotes too high a degree of orientation in the finished film. Toremedy this, one may form a secondary, minor component of lowermolecular weight polymer to reduce extruder backpressure and inhibitmelt fracture. Several industrial processes operate on this principleusing multiple reactor technology to produce a processable bimodalmolecular weight distribution (MWD) high density polyethylene (HDPE)product. HIZEX™, a Mitsui Chemicals HDPE product, is considered theworldwide standard. HIZEX™ is produced in two or more reactors and iscostly to produce. In a multiple reactor process, each reactor producesa single component of the final product.

[0006] Others in the art have tried to produce two polymers together atthe same time in the same reactor using two different catalysts. PCTpatent application WO 99/03899 discloses using a typical metallocenecatalyst and a conventional Ziegler-Natta catalyst in the same reactorto produce a bimodal MWD HDPE. Using two different types of catalysts,however, result in a polymer whose characteristics cannot be predictedfrom those of the polymers that each catalyst would produce if utilizedseparately. This unpredictability occurs, for example, from competitionor other influence between the catalyst or catalyst systems used. Thesepolymers however still do not have a preferred balance of processabilityand strength properties. Thus, there is a desire for a combination ofcatalysts capable of producing processable polyethylene polymers inpreferably a single reactor having desirable combinations of processing,mechanical and optical properties.

SUMMARY OF THE INVENTION

[0007] The present invention provides a catalyst composition, apolymerization process using the catalyst composition, polymer producedtherefrom and products made from the polymer.

[0008] In one embodiment, the invention is directed to a catalystcomposition including at least two metal compounds, where at least onemetal compound is a Group 15 containing metal compound, and where theother metal compound is a bulky ligand metallocene-type compound, aconventional transition metal catalyst, or combinations thereof.

[0009] In one embodiment, the invention is directed to a catalystcomposition including at least two metal compounds, where at least onemetal compound is a Group 15 containing bidentate or tridentate ligatedGroup 3 to 14 metal compound, preferably a Group 3 to 7, more preferablya Group 4 to 6, and even more preferably a Group 4 metal compound, andwhere the other metal compound is a bulky ligand metallocene-typecompound, a conventional transition metal catalyst, or combinationsthereof. In this embodiment it is preferred that the other metalcompound is a bulky ligand metallocene-type compound.

[0010] In another embodiment, the invention is directed to a catalystcomposition including at least two metal compounds, where one metalcompound is a Group 3 to 14 metal atom bound to at least one leavinggroup and also bound to at least two Group 15 atoms, at least one ofwhich is also bound to a Group 15 or 16 atom through another group, andwhere the second metal compound, is different from the first metalcompound, and is a bulky ligand metallocene-type catalyst, aconventional-type transition metal catalyst, or combinations thereof.

[0011] In an embodiment, the invention is directed to processes forpolymerizing olefin(s) utilizing the above catalyst compositions,especially in a single polymerization reactor.

[0012] In yet another embodiment, the invention is directed to thepolymers prepared utilizing the above catalyst composition, preferablyto a new bimodal MWD HDPE.

DETAILED DESCRIPTION OF THE INVENTION Introduction

[0013] The present invention relates to the use of a mixed catalystcomposition where one of the catalysts is a Group 15 containing metalcompound. Applicants have discovered that using these compounds incombination with another catalyst, preferably a bulky ligand metallocenetype compound, produces a new bimodal MWD HDPE product. Surprisingly,the mixed catalyst composition of the present invention may be utilizedin a single reactor system.

Group 15 Containing Metal Compound

[0014] The mixed catalyst composition of the present invention includesa Group 15 containing metal compound. The Group 15 containing compoundgenerally includes a Group 3 to 14 metal atom, preferably a Group 3 to7, more preferably a Group 4 to 6, and even more preferably a Group 4metal atom, bound to at least one leaving group and also bound to atleast two Group 15 atoms, at least one of which is also bound to a Group15 or 16 atom through another group.

[0015] In one preferred embodiment, at least one of the Group 15 atomsis also bound to a Group 15 or 16 atom through another group which maybe a C₁ to C₂₀ hydrocarbon group, a heteroatom containing group,silicon, germanium, tin, lead, or phosphorus, wherein the Group 15 or 16atom may also be bound to nothing or a hydrogen, a Group 14 atomcontaining group, a halogen, or a heteroatom containing group, andwherein each of the two Group 15 atoms are also bound to a cyclic groupand may optionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

[0016] In a preferred embodiment, the Group 15 containing metal compoundof the present invention may be represented by the formulae:

[0017] wherein

[0018] M is a Group 3 to 12 transition metal or a Group 13 or 14 maingroup metal, preferably a Group 4, 5, or 6 metal, and more preferably aGroup 4 metal, and most preferably zirconium, titanium or hafnium,

[0019] each X is independently a leaving group, preferably, an anionicleaving group, and more preferably hydrogen, a hydrocarbyl group, aheteroatom or a halogen, and most preferably an alkyl.

[0020] y is 0 or 1 (when y is 0 group L′ is absent),

[0021] n is the oxidation state of M, preferably +3, +4, or +5, and morepreferably +4,

[0022] m is the formal charge of the YZL or the YZL′ ligand, preferably0, −1, −2 or −3, and more preferably −2,

[0023] L is a Group 15 or 16 element, preferably nitrogen,

[0024] L′ is a Group 15 or 16 element or Group 14 containing group,preferably carbon, silicon or germanium,

[0025] Y is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0026] Z is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0027] R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, aheteroatom containing group having up to twenty carbon atoms, silicon,germanium, tin, lead, or phosphorus, preferably a C₂ to C₂₀ alkyl, arylor aralkyl group, more preferably a linear, branched or cyclic C₂ to C₂₀alkyl group, most preferably a C₂ to C₆ hydrocarbon group.

[0028] R³ is absent or a hydrocarbon group, hydrogen, a halogen, aheteroatom containing group, preferably a linear, cyclic or branchedalkyl group having 1 to 20 carbon atoms, more preferably R³ is absent,hydrogen or an alkyl group, and most preferably hydrogen

[0029] R⁴ and R⁵ are independently an alkyl group, an aryl group,substituted aryl group, a cyclic alkyl group, a substituted cyclic alkylgroup, a cyclic aralkyl group, a substituted cyclic aralkyl group ormultiple ring system, preferably having up to 20 carbon atoms, morepreferably between 3 and 10 carbon atoms, and even more preferably a C₁to C₂₀ hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀ aralkylgroup, or a heteroatom containing group, for example PR₃, where R is analkyl group,

[0030] R¹ and R² may be interconnected to each other, and/or R⁴ and R⁵may be interconnected to each other,

[0031] R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclicor branched alkyl group having 1 to 20 carbon atoms, more preferablyabsent, and

[0032] R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, a heteroatom containing group.

[0033] By “formal charge of the YZL or YZL′ ligand”, it is meant thecharge of the entire ligand absent the metal and the leaving groups X.

[0034] By “R¹ and R² may also be interconnected” it is meant that R¹ andR² may be directly bound to each other or may be bound to each otherthrough other groups. By “R⁴ and R⁵ may also be interconnected” it ismeant that R⁴ and R⁵ may be directly bound to each other or may be boundto each other through other groups.

[0035] An alkyl group may be a linear, branched alkyl radicals, oralkenyl radicals, alkynyl radicals, cycloalkyl radicals or arylradicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

[0036] In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

[0037] wherein

[0038] R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, a heteroatom containing group containingup to 40 carbon atoms, preferably a C₁ to C₂₀ linear or branched alkylgroup, preferably a methyl, ethyl, propyl or butyl group, any two Rgroups may form a cyclic group and/or a heterocyclic group. The cyclicgroups may be aromatic. In a preferred embodiment R⁹, R¹⁰ and R¹² areindependently a methyl, ethyl, propyl or butyl group (including allisomers), in a preferred embodiment R⁹, R¹⁰ and R¹² are methyl groups,and R⁸ and R¹¹ are hydrogen.

[0039] In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

[0040] In this embodiment, M is a Group 4 metal, preferably zirconium,titanium or hafnium, and even more preferably zirconium; each of L, Y,and Z is nitrogen; each of R¹ and R² is —CH₂—CH₂—; R³ is hydrogen; andR⁶ and R⁷ are absent.

[0041] In a particularly preferred embodiment the Group 15 containingmetal compound is represented by the formula:

[0042] In compound I, Ph equals phenyl.

[0043] The Group 15 containing metal compounds of the invention areprepared by methods known in the art, such as those disclosed in EP 0893 454 A1, U.S. Pat. No. 5,889,128 and the references cited in U.S.Pat. No. 5,889,128 which are all herein incorporated by reference. U.S.application Ser. No. 09/312,878, filed May 17, 1999, discloses a gas orslurry phase polymerization process using a supported bisamide catalyst,which is also incorporated herein by reference.

[0044] A preferred direct synthesis of these compounds comprisesreacting the neutral ligand, (see for example YZL or YZL′ of formula 1or 2) with M^(n)X_(n) (M is a Group 3 to 14 metal, n is the oxidationstate of M, each X is an anionic group, such as halide, in anon-coordinating or weakly coordinating solvent, such as ether, toluene,xylene, benzene, methylene chloride, and/or hexane or other solventhaving a boiling point above 60° C., at about 20 to about 150° C.(preferably 20 to 100° C.), preferably for 24 hours or more, thentreating the mixture with an excess (such as four or more equivalents)of an alkylating agent, such as methyl magnesium bromide in ether. Themagnesium salts are removed by filtration, and the metal complexisolated by standard techniques.

[0045] In one embodiment the Group 15 containing metal compound isprepared by a method comprising reacting a neutral ligand, (see forexample YZL or YZL′ of formula 1 or 2) with a compound represented bythe formula M^(n)X_(n) (where M is a Group 3 to 14 metal, n is theoxidation state of M, each X is an anionic leaving group) in anon-coordinating or weakly coordinating solvent, at about 20° C. orabove, preferably at about 20 to about 100° C., then treating themixture with an excess of an alkylating agent, then recovering the metalcomplex. In a preferred embodiment the solvent has a boiling point above60° C., such as toluene, xylene, benzene, and/or hexane. In anotherembodiment the solvent comprises ether and/or methylene chloride, eitherbeing preferable.

Bulky Ligand Metallocene-Type Compound

[0046] In addition to the Group 15 containing metal compound, the mixedcatalyst composition of the present invention also includes a secondmetal compound, which is preferably a bulky ligand metallocene-typecompound.

[0047] Generally, bulky ligand metallocene-type compounds include halfand full sandwich compounds having one or more bulky ligands bonded toat least one metal atom. Typical bulky ligand metallocene-type compoundsare generally described as containing one or more bulky ligand(s) andone or more leaving group(s) bonded to at least one metal atom. In onepreferred embodiment, at least one bulky ligands is η-bonded to themetal atom, most preferably η⁵-bonded to the metal atom.

[0048] The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

[0049] In one embodiment, the bulky ligand metallocene-type catalystcompounds are represented by the formula:

L^(A)L^(B)MQ_(n)  (III)

[0050] where M is a metal atom from the Periodic Table of the Elementsand may be a Group 3 to 12 metal or from the lanthanide or actinideseries of the Periodic Table of Elements, preferably M is a Group 4, 5or 6 transition metal, more preferably M is a Group 4 transition metal,even more preferably M is zirconium, hafnium or titanium. The bulkyligands, L^(A) and L^(B), are open, acyclic or fused ring(s) or ringsystem(s) and are any ancillary ligand system, including unsubstitutedor substituted, cyclopentadienyl ligands or cyclopentadienyl-typeligands, heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding. In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (III) only one of either L^(A) or L^(B) is present.

[0051] Independently, each L^(A) and L^(B) may be unsubstituted orsubstituted with a combination of substituent groups R. Non-limitingexamples of substituent groups R include one or more from the groupselected from hydrogen, or linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Non-limiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other hydrocarbyl radicals includefluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

[0052] Other ligands may be bonded to the metal M, such as at least oneleaving group Q. In one embodiment, Q is a monoanionic labile ligandhaving a sigma-bond to M. Depending on the oxidation state of the metal,the value for n is 0, 1 or 2 such that formula (III) above represents aneutral bulky ligand metallocene-type catalyst compound.

[0053] Non-limiting examples of Q ligands include weak bases such asamines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicalshaving from 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

[0054] In one embodiment, the bulky ligand metallocene-type catalystcompounds of the invention include those of formula (III) where L^(A)and L^(B) are bridged to each other by at least one bridging group, A,such that the formula is represented by

L^(A)AL^(B)MQ_(n)  (IV)

[0055] These bridged compounds represented by formula (IV) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene-type catalyst compounds of formula (IV) have two or morebridging groups A (EP 664 301 B1).

[0056] In one embodiment, the bulky ligand metallocene-type catalystcompounds are those where the R substituents on the bulky ligands L^(A)and L^(B) of formulas (III) and (IV) are substituted with the same ordifferent number of substituents on each of the bulky ligands. Inanother embodiment, the bulky ligands L^(A) and L^(B) of formulas (III)and (IV) are different from each other.

[0057] Other bulky ligand metallocene-type catalyst compounds andcatalyst systems useful in the invention may include those described inU.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022,5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401,5,723,398, 5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158,5,900,517 and 5,939,503 and PCT publications WO 93/08221, WO 93/08199,WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO99/02540 and WO 99/14221 and European publications EP-A-0 578 838,EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834,EP-B1-0 632 819, EP-B1-0 748 821 and EP-B1-0 757 996, all of which areherein fully incorporated by reference.

[0058] In one embodiment, bulky ligand metallocene-type catalystscompounds useful in the invention include bridged heteroatom, mono-bulkyligand metallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, W096/00244, WO 97/15602 and WO99/20637 and U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401,5,227,440 and 5,264,405 and European publication EPA-0 420 436, all ofwhich are herein fully incorporated by reference.

[0059] In this embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(C)AJMQ_(n)  (V)

[0060] where M is a Group 3 to 16 metal atom or a metal selected fromthe Group of actinides and lanthanides of the Periodic Table ofElements, preferably M is a Group 4 to 12 transition metal, and morepreferably M is a Group 4, 5 or 6 transition metal, and most preferablyM is a Group 4 transition metal in any oxidation state, especiallytitanium; L^(C) is a substituted or unsubstituted bulky ligand bonded toM; J is bonded to M; A is bonded to M and J; J is a heteroatom ancillaryligand; and A is a bridging group; Q is a univalent anionic ligand; andn is the integer 0,1 or 2. In formula (V) above, L^(C), A and J form afused ring system. In an embodiment, L^(C) of formula (V) is as definedabove for L^(A), A, M and Q of formula (V) are as defined above informula (III).

[0061] In formula (V) J is a heteroatom containing ligand in which J isan element with a coordination number of three from Group 15 or anelement with a coordination number of two from Group 16 of the PeriodicTable of Elements. Preferably J contains a nitrogen, phosphorus, oxygenor sulfur atom with nitrogen being most preferred.

[0062] In an embodiment of the invention, the bulky ligandmetallocene-type catalyst compounds are heterocyclic ligand complexeswhere the bulky ligands, the ring(s) or ring system(s), include one ormore heteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene-type catalyst compounds are describedin WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874005 and U.S. Pat. Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611,5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporatedby reference.

[0063] In one embodiment, the bulky ligand metallocene-type catalystcompounds are those complexes known as transition metal catalysts basedon bidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene-type catalyst compounds are those describedin PCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

[0064] In a preferred embodiment, the bulky ligand type metallocene-typecatalyst compound is a complex of a metal, preferably a transitionmetal, a bulky ligand, preferably a substituted or unsubstitutedpi-bonded ligand, and one or more heteroallyl moieties, such as thosedescribed in U.S. Pat. Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057,all of which are herein fully incorporated by reference.

[0065] In a particularly preferred embodiment, the other metal compoundor second metal compound is the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(D)MQ₂(YZ)X_(n)  (VI)

[0066] where M is a Group 3 to 16 metal, preferably a Group 4 to 12transition metal, and most preferably a Group 4, 5 or 6 transitionmetal; L^(D) is a bulky ligand that is bonded to M; each Q isindependently bonded to M and Q₂(YZ) forms a ligand, preferably aunicharged polydentate ligand; A or Q is a univalent anionic ligand alsobonded to M; X is a univalent anionic group when n is 2 or X is adivalent anionic group when n is 1; n is 1 or 2.

[0067] In formula (VI), L and M are as defined above for formula (III).Q is as defined above for formula (III), preferably Q is selected fromthe group consisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Zis selected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃,—PR₂, —H, and substituted or unsubstituted aryl groups, with the provisothat when Q is —NR— then Z is selected from one of the group consistingof —OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

[0068] In a particularly preferred embodiment the bulky ligandmetallocene-type compound is represented by the formula:

Activator and Activation Methods

[0069] The metal compounds described herein are preferably combined withone or more activators to form an olefin polymerization catalyst system.

[0070] For the purposes of this patent specification and appendedclaims, the term “activator” is defined to be any compound or componentor method which can activate any of the Group 15 containing metalcompounds and/or the bulky ligand metallocene-type catalyst compounds ofthe invention as described above. Non-limiting activators, for examplemay include a Lewis acid or a non-coordinating ionic activator orionizing activator or any other compound including Lewis bases, aluminumalkyls, conventional-type cocatalysts and combinations thereof that canconvert a neutral bulky ligand metallocene-type catalyst compound orGroup 15 containing metal compound to a catalytically active Group 15containing metal compound or bulky ligand metallocene-type cation. It iswithin the scope of this invention to use alumoxane or modifiedalumoxane as an activator, and/or to also use ionizing activators,neutral or ionic, such as tri (n-butyl) ammonium tetrakis(pentafluorophenyl) boron, a trisperfluorophenyl boron metalloidprecursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983) or combinationthereof, that would ionize the neutral bulky ligand metallocene-typecatalyst and/or the Group 15 containing metal compound.

[0071] In one embodiment, an activation method using ionizing ioniccompounds not containing an active proton but capable of producing aGroup 15 containing metal compound cation or bulky ligandmetallocene-type catalyst cation and their non-coordinating anion arealso contemplated, and are described in EP-A-0 426 637, EP-A-0 573 403and U.S. Pat. No. 5,387,568, which are all herein incorporated byreference.

[0072] There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166,5,856,256 and 5,939,346 and European publications EP-A-0 561 476,EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCT publicationWO 94/10180, all of which are herein fully incorporated by reference.

[0073] Organoaluminum compounds useful as activators includetrimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum and the like.

[0074] Ionizing compounds may contain an active proton, or some othercation associated with but not coordinated to or only looselycoordinated to the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

[0075] Other activators include those described in PCT publication WO98/07515 such as tris (2,2′,2″-nonafluorobiphenyl) fluoroaluminate,which publication is fully incorporated herein by reference.Combinations of activators are also contemplated by the invention, forexample, alumoxanes and ionizing activators in combinations, see forexample, EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference. WO 98/09996 incorporated herein by referencedescribes activating bulky ligand metallocene-type catalyst compoundswith perchlorates, periodates and iodates including their hydrates. WO98/30602 and WO 98/30603 incorporated by reference describe the use oflithium (2,2′-bisphenyl-ditrimethylsilicate).4THF as an activator for abulky ligand metallocene-type catalyst compound. WO 99/18135incorporated herein by reference describes the use oforgano-boron-aluminum acitivators. EP-B1-0 781 299 describes using asilylium salt in combination with a non-coordinating compatible anion.Also, methods of activation such as using radiation (see EP-B1-0 615 981herein incorporated by reference), electro-chemical oxidation, and thelike are also contemplated as activating methods for the purposes ofrendering the neutral bulky ligand metallocene-type catalyst compound orprecursor to a bulky ligand metallocene-type cation capable ofpolymerizing olefins. Other activators or methods for activating a bulkyligand metallocene-type catalyst compound are described in for example,U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO99/42467 (dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide), which are herein incorporated by reference.

[0076] It is also within the scope of this invention that the abovedescribed Group 15 containing metal compounds and bulky ligandmetallocene-type catalyst compounds can be combined with one or more ofthe catalyst compounds represented by formulas (III) through (VI) withone or more activators or activation methods described above.

[0077] It is also contemplated that any one of the bulky ligandmetallocene-type catalyst compounds of the invention have at least onefluoride or fluorine containing leaving group as described in U.S.application Ser. No. 09/191,916 filed Nov. 13, 1998.

[0078] In a preferred embodiment modified alumoxanes are combined withthe first and second metal compounds of the invention to form a catalystsystem. In a preferred embodiment MMAO3A (modified methyl alumoxane inheptane, commercially available from Akzo Chemicals, Inc., Holland,under the trade name Modified Methylalumoxane type 3A, see for examplethose aluminoxanes disclosed in U.S. Pat. No. 5,041,584, which is hereinincorporated by reference) is combined with the first and second metalcompounds to form a catalyst system.

[0079] The first and second metal compounds may be combined at molarratios of 1:1000 to 1000:1, preferably 1:99 to 99:1, preferably 10:90 to90:10, more preferably 20:80 to 80:20, more preferably 30:70 to 70:30,more preferably 40:60 to 60:40. The particular ratio chosen will dependon the end product desired and/or the method of activation.

[0080] In a particular embodiment, when using, the metal compoundsrepresented by Formula 1 and Formula 2, where both are activated withthe same activator, the preferred weight percents, based upon the weightof the two metal compounds, but not the activator or any support, are 10to 95 weight % compound of formula 1 and 5 to 90 weight % compound offormula 2, preferably 50 to 90 weight % compound of Formula 1 and 10 to50 weight % compound of formula 2, more preferably 60 to 80 weight %compound of formula 1 to 40 to 20 weight % compound of formula 2. In aparticularly preferred embodiment the compound of Formula 2 is activatedwith methylalumoxane, then combined with the compound of Formula 2, theninjected in the reactor.

[0081] In one particular embodiment, when using Compound I and indenylzirconium tris-pivalate where both are activated with the sameactivator, the preferred weight percents, based upon the weight of thetwo catalysts, but not the activator or any support, are 10 to 95 weight% Compound I and 5 to 90 weight % indenyl zirconium trispivalate,preferably 50 to 90 weight % Compound I and 10 to 50 weight % indenylzirconium tris-pivalate, more preferably 60-80 weight % Compound I to 40to 20 weight % indenyl zirconium tris-pivalate. In a particularlypreferred embodiment the indenyl zirconium tris-pivalate is activatedwith methylalumoxane, then combined with Compound I, then injected inthe reactor.

[0082] In general the combined metal compounds and the activator arecombined in ratios of about 1000:1 to about 0.5:1. In a preferredembodiment the metal compounds and the activator are combined in a ratioof about 300:1 to about 1:1, preferably about 150:1 to about 1:1, forboranes, borates, aluminates, etc. the ratio is preferably about 1:1 toabout 10:1 and for alkyl aluminum compounds (such as diethylaluminumchloride combined with water) the ratio is preferably about 0.5:1 toabout 10:1.

Conventional-Type Catalyst Systems Combinable With Formulae I and II

[0083] The mixed catalyst composition of the present invention mayalternately include the Group 15 containing metal compound, as describedabove, and a conventional-type transition catalyst.

[0084] Conventional-type transition metal catalysts are thosetraditional Ziegler-Natta, vanadium and Phillips-type catalysts wellknown in the art. Such as, for example Ziegler-Natta catalysts asdescribed in Ziegler-Natta Catalysts and Polymerizations, John Boor,Academic Press, New York, 1979. Examples of conventional-type transitionmetal catalysts are also discussed in U.S. Pat. Nos. 4,115,639,4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741 allof which are herein fully incorporated by reference. Theconventional-type transition metal catalyst compounds that may be usedin the present invention include transition metal compounds from Groups3 to 17, preferably 4 to 12, more preferably 4 to 6 of the PeriodicTable of Elements.

[0085] These conventional-type transition metal catalysts may berepresented by the formula: MR_(x), where M is a metal from Groups 3 to17, preferably Group 4 to 6, more preferably Group 4, most preferablytitanium; R is a halogen or a hydrocarbyloxy group; and x is theoxidation state of the metal M. Non-limiting examples of R includealkoxy, phenoxy, bromide, chloride and fluoride. Non-limiting examplesof conventional-type transition metal catalysts where M is titaniuminclude TiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl, Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl,Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂, TiCl₃.1/3AlCl₃ and Ti(OC₁₂H₂₅)Cl₃.

[0086] Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred.

[0087] British Patent Application 2,105,355 and U.S. Pat. No. 5,317,036,herein incorporated by reference, describes various conventional-typevanadium catalyst compounds. Non-limiting examples of conventional-typevanadium catalyst compounds include vanadyl trihalide, alkoxy halidesand alkoxides such as VOCl₃, VOCl₂(OBu) where Bu=butyl and VO(OC₂H₅)₃;vanadium tetra-halide and vanadium alkoxy halides such as VCl₄ andVCl₃(OBu); vanadium and vanadyl acetyl acetonates and chloroacetylacetonates such as V(AcAc)₃ and VOCl₂(AcAc) where (AcAc) is an acetylacetonate. The preferred conventional-type vanadium catalyst compoundsare VOCl₃, VCl₄ and VOCl₂—OR where R is a hydrocarbon radical,preferably a C₁ to C₁₀ aliphatic or aromatic hydrocarbon radical such asethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl,tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

[0088] Conventional-type chromium catalyst compounds, often referred toas Phillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, which areherein fully incorporated by reference.

[0089] Still other conventional-type transition metal catalyst compoundsand catalyst systems suitable for use in the present invention aredisclosed in U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062,4,379,758, 5,066,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164 and5,869,585 and published EP-A2 0 416 815 A2 and EP-A1 0 420 436, whichare all herein incorporated by reference.

[0090] Other catalysts may include cationic catalysts such as AlCl₃, andother cobalt, iron, nickel and palladium catalysts well known in theart. See for example U.S. Pat. Nos. 3,487,112, 4,472,559, 4,182,814 and4,689,437 all of which are incorporated herein by reference.

[0091] Typically, these conventional-type transition metal catalystcompounds excluding some conventional-type chromium catalyst compoundsare activated with one or more of the conventional-type cocatalystsdescribed below. Also conventional type transition metal catalysts canbe activated using the activators described above in this patentspecification as appreciated by one in the art.

[0092] Conventional-type cocatalyst compounds for the aboveconventional-type transition metal catalyst compounds may be representedby the formula M³M⁴ _(v)X² _(c)R³ _(b-c), wherein M³ is a metal fromGroup 1 to 3 and 12 to 13 of the Periodic Table of Elements; M⁴ is ametal of Group 1 of the Periodic Table of Elements; v is a number from 0to 1; each X² is any halogen; c is a number from 0 to 3; each R³ is amonovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4;and wherein b minus c is at least 1. Other conventional-typeorganometallic cocatalyst compounds for the above conventional-typetransition metal catalysts have the formula M³R³ _(k), where M³ is aGroup IA, IIA, IIB or IIIA metal, such as lithium, sodium, beryllium,barium, boron, aluminum, zinc, cadmium, and gallium; k equals 1, 2 or 3depending upon the valency of M³ which valency in turn normally dependsupon the particular Group to which M³ belongs; and each R³ may be anymonovalent hydrocarbon radical.

[0093] Non-limiting examples of conventional-type organometalliccocatalyst compounds useful with the conventional-type catalystcompounds described above include methyllithium, butyllithium,dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium,diethylzinc, tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium,di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminumalkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylaluminum,and tri-isobutylaluminum. Other conventional-type cocatalyst compoundsinclude monoorganohalides and hydrides of Group 2 metals, and mono- ordi-organohalides and hydrides of Group 3 and 13 metals. Non-limitingexamples of such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide,di-isobutylaluminum hydride, methylcadmium hydride, diethylboronhydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesiumhydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminumhydride and bromocadmium hydride. Conventional-type organometalliccocatalyst compounds are known to those in the art and a more completediscussion of these compounds may be found in U.S. Pat. Nos. 3,221,002and 5,093,415, which are herein fully incorporated by reference.

Polymerization Process

[0094] The metal compounds, mixed metal compounds and catalyst systemsdescribed above are suitable for use in any polymerization process,including solution, gas or slurry processes or a combination thereof.The polymerization process is preferably a gas or slurry phase processand more preferably utilizes a single reactor, and most preferably asingle gas phase reactor.

[0095] In a preferred embodiment, the catalyst system consists of themetal compounds (catalyst) and or the activator (cocatalyst) which arepreferably introduced into the reactor in solution. Solutions of themetal compounds are prepared by taking the catalyst and dissolving it inany suitable solvent such as an alkane, toluene, xylene, etc. Thesolvent may first be purified in order to remove any poisons, which mayaffect the catalyst activity, including any trace water and/oroxygenated compounds. Purification of the solvent may be accomplished byusing activated alumina and activated supported copper catalyst. Thecatalyst is preferably completely dissolved into the solution to form ahomogeneous solution. Both catalysts may be dissolved into the samesolvent, if desired. Once the catalysts are in solution, they may bestored indefinitely until use.

[0096] For polymerization, it preferred that the catalyst is combinedwith an activator prior to introduction into the reactor. Additionally,other solvents and reactants can be added to the catalyst solutions(on-line or off-line), to the activator (on-line or off-line), or to theactivated catalyst or catalysts. See U.S. Pat. Nos. 5,317,036 and5,693,727, EP-A-0 593 083, and WO 97/46599 which are fully incorporatedherein by reference, that describe solution feed systems to a reactor.There are many different configurations which are possible to combinethe catalysts and activator.

[0097] The catalyst system, the metal compounds and or the activator arepreferably introduced into the reactor in one or more solutions. Themetal compounds may be activated independently, in series or together.In one embodiment a solution of the two activated metal compounds in analkane such as pentane, hexane, toluene, isopentane or the like isintroduced into a gas phase or slurry phase reactor. In anotherembodiment the catalysts system or the components can be introduced intothe reactor in a suspension or an emulsion. In one embodiment, thesecond metal compound is contacted with the activator, such as modifiedmethylalumoxane, in a solvent and just before the solution is fed into agas, slurry or solution phase reactor. A solution of the Group 15containing metal compound is combined with a solution of the secondcompound and the activator and then introduced into the reactor.

[0098] In the following illustrations, A refers to a catalyst or mixtureof catalysts, and B refers to a different catalyst or mixture ofcatalysts. The mixtures of catalysts in A and B can be the samecatalysts, just in different ratios. Further, it is noted thatadditional solvents or inert gases may be added at many locations.

[0099] Illustration 1: A and B plus the activator are mixed off-line andthen fed to the reactor.

[0100] Illustration 2: A and B are mixed off-line. Activator is addedin-line and then fed to the reactor.

[0101] Illustration 3: A or B is contacted with the activator (off-line)and then either A or B is added in-line before entering the reactor.

[0102] Illustration 4: A or B is contacted with the activator (on-line)and then either A or B is added in-line before entering the reactor.

[0103] Illustration 5: A and B are each contacted with the activatoroff-line. Then A and activator and B and activator are contacted in linebefore entering the reactor.

[0104] Illustration 6: A and B are each contacted with the activatorin-line. Then A and activator and B and activator are contacted in-linebefore entering the reactor. (This is a preferred configuration sincethe ratio of A to B and the ratio of activator to A and the ratio ofactivator to B can be controlled independently.)

[0105] Illustration 7: In this example, A or B is contacted with theactivator (on-line) while a separate solution of either A or B iscontacted with activator off-line. Then both stream of A or B andactivator are contacted in-line before entering the reactor.

[0106] Illustration 8: A is contacted on-line with B. Then, an activatoris fed to in-line to the A and B mixture.

[0107] Illustration 9: A is activated with activator off-line. Then Aand activator is contacted on-line with B. Then, an activator is fed toin-line to the A and B and activator mixture.

[0108] In one embodiment, this invention is directed toward thepolymerization or copolymerization reactions involving thepolymerization of one or more monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. The invention is particularly well suited to the copolymerizationreactions involving the polymerization of one or more olefin monomers ofethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1,octene-1, decene-1,3-methyl-pentene-1,3,5,5-trimethyl-hexene-1 andcyclic olefins or a combination thereof. Other monomers can includevinyl monomers, diolefins such as dienes, polyenes, norbomene,norbomadiene monomers. Preferably a copolymer of ethylene is produced,where the comonomer is at least one alpha-olefin having from 4 to 15carbon atoms, preferably from 4 to 12 carbon atoms, more preferably from4 to 8 carbon atoms and most preferably from 4 to 7 carbon atoms. In analternate embodiment, the geminally disubstituted olefins disclosed inWO 98/37109 may be polymerized or copolymerized using the inventionherein described.

[0109] In another embodiment ethylene or propylene is polymerized withat least two different comonomers to form a terpolymer. The preferredcomonomers are a combination of alpha-olefin monomers having 4 to 10carbon atoms, more preferably 4 to 8 carbon atoms, optionally with atleast one diene monomer. The preferred terpolymers include thecombinations such as ethylene/butene-1/hexene-1,ethylene/propylene/butene-1, propylene/ethylene/hexene-1,ethylene/propylene/norbomene and the like.

[0110] In a particularly preferred embodiment the process of theinvention relates to the polymerization of ethylene and at least onecomonomer having from 4 to 8 carbon atoms, preferably 4 to 7 carbonatoms. Particularly, the comonomers are butene-1,4-methyl-pentene-1,hexene-1 and octene-1, the most preferred being hexene-1 and/orbutene-1.

[0111] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228 all of which are fully incorporated herein byreference.)

[0112] The reactor pressure in a gas phase process may vary from about10 psig (69 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 100 psig (690 kPa) to about 400 psig (2759 kPa),preferably in the range of from about 200 psig (1379 kPa) to about 400psig (2759 kPa), more preferably in the range of from about 250 psig(1724 kPa) to about 350 psig (2414 kPa).

[0113] The reactor temperature in the gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 75° C. to 110° C.,and most preferably in the range of from about 85° C. to about 110° C.Altering the polymerization temperature can also be used as a tool toalter the final polymer product properties.

[0114] The productivity of the catalyst or catalyst system is influencedby the main monomer partial pressure. The preferred mole percent of themain monomer, ethylene or propylene, preferably ethylene, is from about25 to 90 mole percent and the monomer partial pressure is in the rangeof from about 75 psia (517 kPa) to about 300 psia (2069 kPa), which aretypical conditions in a gas phase polymerization process. In oneembodiment the ethylene partial pressure is about 220 to 240 psi(1517-1653 kPa). In another embodiment the molar ratio of hexene toethylene ins the reactor is 0.03:1 to 0.08:1.

[0115] In a preferred embodiment, the reactor utilized in the presentinvention and the process of the invention produce greater than 500 lbsof polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr)or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr),more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even morepreferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

[0116] Other gas phase processes contemplated by the process of theinvention include those described in U.S. Pat. Nos. 5,627,242, 5,665,818and 5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202and EP-B-634 421 all of which are herein fully incorporated byreference.

[0117] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0118] In one embodiment, a preferred polymerization technique of theinvention is referred to as a particle form polymerization, or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 185° F. (85° C.) toabout 230° F. (110° C.). Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in U.S. Pat. No. 4,613,484, which is herein fullyincorporated by reference.

[0119] In another embodiment, the slurry process is carried outcontinuously in a loop reactor. The catalyst as a solution, as asuspension, as an emulsion, as a slurry in isobutane or as a dry freeflowing powder is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. The reactor ismaintained at pressure of about 525 psig to 625 psig (3620 kPa to 4309kPa) and at a temperature in the range of about 140° F. to about 220° F.(about 60° C. to about 104° C.) depending on the desired polymerdensity. Reaction heat is removed through the loop wall since much ofthe reactor is in the form of a double-jacketed pipe. The slurry isallowed to exit the reactor at regular intervals or continuously to aheated low pressure flash vessel, rotary dryer and a nitrogen purgecolumn in sequence for removal of the isobutane diluent and allunreacted monomer and comonomers. The resulting hydrocarbon free powderis then compounded for use in various applications.

[0120] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0121] In another embodiment in the slurry process of the invention thetotal reactor pressure is in the range of from 400 psig (2758 kPa) to800 psig (5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig(4827 kPa), more preferably 500 psig (3448 kPa) to about 650 psig (4482kPa), most preferably from about 525 psig (3620 kPa) to 625 psig (4309kPa).

[0122] In yet another embodiment in the slurry process of the inventionthe concentration of ethylene in the reactor liquid medium is in therange of from about 1 to 10 weight percent, preferably from about 2 toabout 7 weight percent, more preferably from about 2.5 to about 6 weightpercent, most preferably from about 3 to about 6 weight percent.

[0123] A preferred process of the invention is where the process,preferably a slurry or gas phase process is operated in the absence ofor essentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This preferredprocess is described in PCT publication WO 96/08520 and U.S. Pat. No.5,712,352, which are herein fully incorporated by reference.

[0124] In a preferred embodiment of the invention, a slurry of analuminum distearate in mineral oil is introduced into the reactor,separately or with the first and or second metal complex and/or with anactivator, from the metal compounds and or the activators. Moreinformation on using aluminum stearate type additives may be found inU.S. application Ser. No. 09/113,261 filed Jul. 10, 1998, which isincorporated by reference herein.

[0125] In an embodiment, if the second metal compound and Group 15 metalcompound of the catalyst system are introduced to the reactor in series,it is preferably that the second metal compound is added and/oractivated first and that the Group 15 metal compound is added and/oractivated second.

[0126] In another embodiment, the residence time of the catalystcomposition is between about 3 to about 6 hours and preferably betweenabout 3.5 and about 5 hours.

[0127] In an embodiment, the mole ratio of comonomer to ethylene,C_(x)/C₂, where C_(x) is the amount of comonomer and C₂ is the amount ofethylene is between about 0.001 to 0.0100 and more preferably betweenabout 0.002 to 0.008.

[0128] The melt index (and other properties) of the polymer produced maybe changed by manipulating hydrogen concentration in the polymerizationsystem by:

[0129] 1.) changing the amount of the first catalyst in thepolymerization system, and/or

[0130] 2.) changing the amount of the second catalyst in thepolymerization system, and/or

[0131] 3.) adding hydrogen to the polymerization process; and/or

[0132] 4.) changing the amount of liquid and/or gas that is withdrawnand/or purged from the process; and/or

[0133] 5.) changing the amount and/or composition of a recovered liquidand/or recovered gas returned to the polymerization process, saidrecovered liquid or recovered gas being recovered from polymerdischarged from the polymerization process; and/or

[0134] 6.) using a hydrogenation catalyst in the polymerization process;and/or

[0135] 7.) changing the polymerization temperature; and/or

[0136] 8.) changing the ethylene partial pressure in the polymerizationprocess; and/or

[0137] 9.) changing the ethylene to hexene ratio in the polymerizationprocess; and/or

[0138] 10.) changing the activator to transition metal ratio in theactivation sequence.

[0139] The hydrogen concentration in the reactor is about 100 to 5000ppm, preferably 200 to 2000 ppm, more preferably 250 to 1900 ppm, morepreferably 300 to 1800 ppm, and more preferably 350 to 1700 ppm, morepreferably 400 to 1600 ppm, more preferably 500 to 1500 ppm, morepreferably 500 to 1400 ppm, more preferably 500 to 1200 ppm, morepreferably 600 to 1200 ppm, preferably 700 to 1100 ppm, and morepreferably 800 to 1000 ppm. The hydrogen concentration in the reactorbeing inversely proportional to the polymer's weight average molecularweight (M_(W)).

[0140] The catalyst and/or the activator may be placed on, deposited on,contacted with, incorporated within, adsorbed, or absorbed in a support.Typically the support is any of the solid, porous supports, includingmicroporous supports. Typical support materials include talc; inorganicoxides such as silica, magnesium chloride, alumina, silica-alumina;polymeric supports such as polyethylene, polypropylene, polystyrene,cross-linked polystyrene; and the like. Preferably the support is usedin finely divided form. Prior to use the support is preferably partiallyor completely dehydrated. The dehydration may be done physically bycalcining or by chemically converting all or part of the activehydroxyls. For more information on how to support catalysts, see U.S.Pat. No. 4,808,561 which discloses how to support a metallocene catalystsystem. In addition, there are various other techniques of supportingcatalysts as are well known in the art. Methods for supporting the Group15 metal compound of the invention are described in U.S. applicationSer. No. 09/312,878, filed May 17, 1999 which is herein incorporated byreference.

Polymer of the Invention

[0141] The new polymers produced by the process of the present inventionmay be used in a wide variety of products and end use applications.Preferably the new polymers include polyethylene, and even morepreferably include bimodal polyethylene produced in a single reactor. Inaddition to bimodal polymers, it is not beyond the scope of the presentapplication to produce a unimodal or multi-modal polymer.

[0142] The Group 15 containing metal compound, when used alone, producesa high weight average molecular weight M_(w) polymer (such as forexample above 100,000, preferably above 150,000, preferably above200,000, preferably above 250,000, more preferably above 300,000). Thesecond metal compound, when used alone, produces a low molecular weightpolymer (such as for example below 80,000, preferably below 70,000,preferably below 60,000, more preferably below 50,000, more preferablybelow 40,000, more preferably below 30,000, more preferably below 20,000and above 5,000, more preferably below 20,000 and above 10,000).

[0143] The polyolefins, particularly polyethylenes, produced by thepresent invention, have a density of 0.89 to 0.97 g/cm³. Preferably,polyethylenes having a density of 0.910 to 0.965 g/cm³, more preferably0.915 to 0.960 g/cm³, and even more preferably 0.920 to 0.955 g/cm³ canbe produced. In some embodiments, a density of 0.915 to 0.940 g/cm³would be preferred, in other embodiments densities of 0.930 to 0.970g/cm³ are preferred.

[0144] In a preferred embodiment, the polyolefin recovered typically hasa melt index I₂ (as measured by ASTM D-1238, Condition E at 190° C.) ofabout 0.01 to 1000 dg/min or less. In a preferred embodiment, thepolyolefin is ethylene homopolymer or copolymer. In a preferredembodiment for certain applications, such as films, pipes, moldedarticles and the like, a melt index of 10 dg/min or less is preferred.For some films and molded articles, a melt index of 1 dg/min or less ispreferred. Polyethylene having a I₂ between 0.01 and 10 dg/min ispreferred.

[0145] In a preferred embodiment the polymer produced herein has an I₂₁(as measured by ASTM-D-1238-F, at 190° C.) of 0.1 to 10 dg/min,preferably 0.2 to 7.5 dg/min, preferably 2.0 dg/min or less, preferably1.5 dg/min or less, preferably 1.2 dg/min or less, more preferablybetween 0.5 and 1.0 dg/min, more preferably between 0.6 and 0.8 dg/min.

[0146] In another embodiment, the polymers of the invention have a meltflow index “MIR” of I₂₁/I₂ of 80 or more, preferably 90 or more,preferably 100 or more, preferably 125 or more.

[0147] In another embodiment the polymer has an I₂₁ (as measured by ASTM1238, condition F, at 190° C.)(sometimes referred to as Flow Index) of2.0 dg/min or less, preferably 1.5 dg/min or less, preferably 1.2 dg/minor less, more preferably between 0.5 and 1.0 dg/min, more preferablybetween 0.6 and 0.8 dg/min and an I₂₁/I₂ of 80 or more, preferably 90 ormore, preferably 100 or more, preferably 125 or more and has one or moreof the following properties in addition:

[0148] (a) Mw/Mn of between 15 and 80, preferably between 20 and 60,preferably between 20 and 40. Molecular weight (Mw and Mn) are measuredas described below in the examples section;

[0149] (b) an Mw of 180,000 or more, preferably 200,000 or more,preferably 250,000 or more, preferably 300,000 or more;

[0150] (c) a density (as measured by ASTM 2839) of 0.94 to 0.970 g/cm³;preferably 0.945 to 0.965 g/cm³; preferably 0.950 to 0.960 g/cm³;

[0151] (d) a residual metal content of 5.0 ppm transition metal or less,preferably 2.0 ppm transition metal or less, preferably 1.8 ppmtransition metal or less, preferably 1.6 ppm transition metal or less,preferably 1.5 ppm transition metal or less, preferably 2.0 ppm or lessof Group 4 metal, preferably 1.8 ppm or less of Group 4 metal,preferably 1.6 ppm or less of Group 4 metal, preferably 1.5 ppm or lessof Group 4 metal, preferably 2.0 ppm or less zirconium, preferably 1.8ppm or less zirconium, preferably 1.6 ppm or less zirconium, preferably1.5 ppm or less zirconium(as measured by Inductively Coupled PlasmaOptical Emission Spectroscopy (ICPAES) run against commerciallyavailable standards, where the sample is heated so as to fully decomposeall organics and the solvent comprises nitric acid and, if any supportis present, another acid to dissolve any support (such as hydrofluoricacid to dissolve silica supports) is present;

[0152] (e) 35 weight percent or more high weight average molecularweight component, as measured by size-exclusion chromatography,preferably 40% or more. In a particularly preferred embodiment thehigher molecular weight fraction is present at between 35 and 70 weight%, more preferably between 40 and 60 weight %.

[0153] In a preferred embodiment the catalyst composition describedabove is used to make a polyethylene having a density of between 0.94and 0.970 g/cm³ (as measured by ASTM D 2839) and an 12 of 0.5 or lessg/10 min or less

[0154] In another embodiment the catalyst composition described above isused to make a polyethylene having an I₂₁ of less than 10 and a densityof between about 0.940 and 0.950 g/cm³ or an I₂₁ of less than 20 and adensity of about 0.945 g/cm³ or less.

[0155] In another embodiment, the polymer of the invention is made intoa pipe by methods known in the art. For pipe applications, the polymersof the invention have a I₂₁ of from about 2 to about 10 dg/min andpreferably from about 2 to about 8 dg/min. In another embodiment, thepipe of the invention satisfies ISO qualifications.

[0156] In another embodiment, the catalyst composition of the presentinvention is used to make polyethylene pipe able to withstand at least50 years at an ambient temperature of 20° C., using water as theinternal test medium and either water or air as the outside environment(Hydro static (hoop) stress as measured by ISO TR 9080).

[0157] In another embodiment, the polymer has a notch tensile test(resistance to slow crack growth) result of greater than 150 hours at3.0 MPa, preferably greater than 500hours at 3.0 MPa and more preferablygreater than 600 hours at 3.0 mPa. (as measured by ASTM-F1473).

[0158] In another embodiment, the catalyst composition of the presentinvention is used to make polyethylene pipe having a predicted S-4 T_(c)for 110 mm pipe of less than −5° C., preferably of less than −15° C. andmore preferably less than −40° C. (ISO DIS 13477/ASTM F1589).

[0159] In another embodiment, the polymer has an extrusion rate ofgreater than about 17 lbs/hour/inch of die circumference and preferablygreater than about 20 lbs/hour/inch of die circumference and morepreferably greater than about 22 lbs/hour/inch of die circumference.

[0160] The polyolefins of the invention can be made into films, moldedarticles (including pipes), sheets, wire and cable coating and the like.The films may be formed by any of the conventional techniques known inthe art including extrusion, co-extrusion, lamination, blowing andcasting. The film may be obtained by the flat film or tubular processwhich may be followed by orientation in a uniaxial direction or in twomutually perpendicular directions in the plane of the film to the sameor different extents. Orientation may be to the same extent in bothdirections or may be to different extents. Particularly preferredmethods to form the polymers into films include extrusion or coextrusionon a blown or cast film line.

[0161] In another embodiment, the polymer of the invention is made intoa film by methods known in the art. For film application, the polymersof the invention have a I₂₁ of from about 2 to about 50 dg/min,preferably from about 2 to about 30 dg/min, even more preferably fromabout 2 to about 20 dg/min, still more preferably about 5 to about 15dg/min and yet more preferably from about 5 to about 10 dg/min.

[0162] In another embodiment, the polymer has an MD Tear of 0.5 mil(13μ) film of between about 5 g/mil and 25 g/mil preferably, betweenabout 15 g/mil and 25 g/mil, and more preferably between about 20 g/miland 25 g/mil.

[0163] The films produced may further contain additives such as slip,antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers,antistats, polymer processing aids, neutralizers, lubricants,surfactants, pigrnents, dyes and nucleating agents. Preferred additivesinclude silicon dioxide, synthetic silica, titanium dioxide,polydimethylsiloxane, calcium carbonate, metal stearates, calciumstearate, zinc stearate, talc, BaSO₄, diatomaceous earth, wax, carbonblack, flame retarding additives, low molecular weight resins,hydrocarbon resins, glass beads and the like. The additives may bepresent in the typically effective amounts well known in the art, suchas 0.001 weight % to 10 weight %.

[0164] In another embodiment, the polymer of the invention is made intoa molded article by methods known in the art, for example, by blowmolding and injection-stretch molding. For molded applications, thepolymers of the invention have a I₂₁ of from about 20 dg/min to about 50dg/min and preferably from about 35 dg/min to about 45 dg/min.

[0165] In another embodiment, the polymers of the invention, includingthose described above, have an ash content less than 100 ppm, morepreferably less than 75 ppm, and even more preferably less than 50 ppmis produced. In another embodiment, the ash contains negligibly smalllevels of titanium as measured by Inductively Coupled Plasma/AtomicEmission Spectroscopy (ICPAES) as is well known in the art.

[0166] In another embodiment, the polymers of the invention, contain anitrogen containing ligand detectable by High Resolution MassSpectroscopy (HRMS) as is well known in the art.

EXAMPLES

[0167] In order to provide a better understanding of the presentinvention, including representative advantages thereof, the followingexamples are offered.

[0168] M_(n) and M_(w) were measured by gel permeation chromatography ona waters 150° C. GPC instrument equipped with differential refractionindex detectors. The GPC columns were calibrated by running a series ofmolecular weight standards and the molecular weights were calculatedusing Mark Houwink coefficients for the polymer in question.

[0169] MWD=M_(w)/M_(n).

[0170] Density was measured according to ASTM D 1505.

[0171] Melt Index (MI) I₂ was measured according to ASTM D-1238,Condition E, at 190° C.

[0172] I₂₁ was measured according to ASTM D-1238, Condition F, at 190°C.

[0173] Melt Index Ratio (MIR) is the ratio of I₂₁ over I₂.

[0174] Weight % comonomer was measured by proton NMR.

[0175] Dart Impact was measured according to ASTM D 1709.

[0176] MD and TD Elmendorf Tear were measured according to ASTM D 1922.

[0177] MD and TD 1% Secant modulus were measured according to ASTM D882.

[0178] MD and TD tensile strength and ultimate tensile strength weremeasured according to ASTM D 882.

[0179] MD and TD elongation and ultimate elongation were measuredaccording to ASTM D 412.

[0180] MD and TD Modulus were measured according to ASTM 882-91.

[0181] Haze was measured according to ASTM 1003-95, Condition A.

[0182] 45° gloss was measured according to ASTM D 2457.

[0183] BUR is blow up ratio.

[0184] “PPH” is pounds per hour. “mPPH” is millipounds per hour. “ppmw”is parts per million by weight.

[0185] Indenyl zirconium tris pivalate, a bulky ligand metallocene-typecompound, also represented by formula VI, can be prepared by performingthe following general reactions:

Zr(NEt₂)₄+IndH→IndZr(NEt₂)₃+Et₂NH  (1)

IndZr(NEt₂)₃+3(CH₃)₃CCO₂H→IndZr[O₂CC(CH₃)]₃+Et₂NH  (2)

[0186] Where Ind=indenyl and Et is ethyl.

[0187] Preparation of [(2,4,6-Me₃C₆H₂)NHCH₂CH₂]₂NH Ligand (Ligand I)

[0188] A 2 L one-armed Schlenk flask was charged with a magnetic stirbar, diethylenetriamine (23.450 g, 0.227 mol), 2-bromomesitylene (90.51g, 0.455 mol), tris(dibenzylideneacetone)dipalladium (1.041 g, 1.14mmol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemicBINAP) (2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol),and toluene (800 mL) under dry, oxygen-free nitrogen. The reactionmixture was stirred and heated to 100° C. After 18 h the reaction wascomplete, as judged by proton NMR spectroscopy. All remainingmanipulations can be performed in air. All solvent was removed undervacuum and the residues dissolved in diethyl ether (1 L). The ether waswashed with water (3×250 mL) followed by saturated aqueous NaCl (180 gin 500 mL) and dried over magnesium sulfate (30 g). Removal of the etherin vacuo yielded a red oil which was dried at 70° C. for 12 h undervacuum (yield: 71.10 g, 92%). ¹H NMR (C₆D₆) δ 6.83 (s, 4), 3.39 (br s,2), 2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (br s, 1).

[0189] Preparation of Catalyst A

[0190] Preparation of 1.5 wt % Catalyst A in Toluene Solution

[0191] Note: All procedures below were performed in a glove box.

[0192] 1.) Weighed out 100 grams of purified toluene into a 1 LErlenmeyer flask equipped with a Teflon coated stir bar.

[0193] 2.) Added 7.28 grams of Tetrabenzyl Zirconium.

[0194] 3.) Placed solution on agitator and stirred for 5 minutes. All ofthe solids went into solution.

[0195] 4.) Added 5.42 grams of Ligand I.

[0196] 5.) Added an additional 551 grams of purified toluene and allowedmixture to stir for 15 minutes. No solids remained in the solution.

[0197] 6.) Poured catalyst solution into a clean, purged 1-L Whiteysample cylinder, labeled, removed from glovebox and placed in holdingarea for operations.

[0198] Alternate Preparation of Compound I{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}Zr(CH₂Ph)₂

[0199] A 500 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl zirconium (Boulder Scientific) (41.729 g, 91.56 mmol), and300 mL of toluene under dry, oxygen-free nitrogen. Solid ligand I above(32.773 g, 96.52 mmol) was added with stirring over 1 minute (thedesired compound precipitates). The volume of the slurry was reduced to100 mL and 300 mL of pentane added with stirring. The solidyellow-orange product was collected by filtration and dried under vacuum(44.811 g, 80% yield).

[0200]¹H NMR (C₆D₆) δ 7.22-6.81 (m, 12), 5.90 (d, 2), 3.38 (m, 2), 3.11(m, 2) 3.01 (m, 1), 2.49 (m, 4), 2.43 (s, 6), 2.41 (s, 6), 2.18 (s, 6),1.89 (s, 2), 0.96 (s, 2).

[0201] Preparation of Catalyst B

[0202] Preparation 1 wt % Catalyst B in Hexane Solution

[0203] All procedures were performed in a glove box.

[0204] 1.) Transfer 1 liter of purified hexane into a 1 L Erlenmeyerflask equipped with a Teflon coated stir bar.

[0205] 2.) Add 6.67 grams of indenyl zirconium tris pivalate driedpowder.

[0206] 3.) Place solution on magnetic agitator and stir for 15 minutes.All of the solids go into solution.

[0207] 4.) Pour solution into a clean, purged 1-L Whitey samplecylinder, labeled, and removed from glovebox and place in holding areauntil use in operation.

Comparative Example 1

[0208] An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchangerEthylene was fed to the reactor at a rate of about 40 pounds per hour(18.1 kg/hr), hexene was fed to the reactor at a rate of about 0.6pounds per hour (0.27 kg/hr) and hydrogen was fed to the reactor at arate of 5 MPPH. Nitrogen was fed to the reactor as a make-up gas atabout 5-8 PPH. The production rate was about 27 PPH. The reactor wasequipped with a plenum having about 1,900 PPH of recycle gas flow. (Theplenum is a device used to create a particle lean zone in a fluidizedbed gas-phase reactor, as described in detail in U.S. Pat. No. 5,693,727which is incorporated herein by reference.) A tapered catalyst injectionnozzle having a 0.041 inch (0.10 cm) hole size was positioned in theplenum gas flow. A solution of 1 wt % of Catalyst A in toluene andcocatalyst (MMAO-3A, 1 wt % Aluminum) were mixed in line prior topassing through the injection nozzle into the fluidized bed. (MMAO-3A ismodified methyl alumoxane in heptane, commercially available from AkzoChemicals, Inc. under the trade name Modified Methylalumoxane type 3A.)MMAO to catalyst was controlled so that the Al:Zr molar ratio was 400:1.Nitrogen and isopentane were also fed to the injection nozzle as neededto maintain a stable average particle size. A unimodal polymer havingnominal 0.28 dg/min (I₂₁) and 0.935 g/cc (density) properties wasobtained. A residual zirconium of 1.63 ppmw was calculated based on areactor mass balance.

Comparative Example 2

[0209] An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 80° C. and 320 psig(2.2 MPa) total reactor pressure having a water cooled heat exchangerEthylene was fed to the reactor at a rate of about 37 pounds per hour(19.8 kg/hr), hexene was fed to the reactor at a rate of about 0.4pounds per hour (0.18 kg/hr) and hydrogen was fed to the reactor at arate of 12 mPPH. Ethylene was fed to maintain 180 psi (1.2 MPa) ethylenepartial pressure in the reactor. The production rate was about 25 PPH.The reactor was equipped with a plenum having about 1,030 PPH of recyclegas flow. (The plenum is a device used to create a particle lean zone ina fluidized bed gas-phase reactor.) A tapered catalyst injection nozzlehaving a 0.055 inch (0.14 cm) hole size was positioned in the plenum gasflow. A solution of 1 wt % Catalyst B in hexane catalyst was mixed with0.2 lb/hr (0.09 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube for about 15 minutes. The Catalyst B and hexenemixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a linefor about 40 minutes. In addition to the solution, isopentane andnitrogen were added to control particle size. The total system waspassed through the injection nozzle into the fluidized bed. MMAO tocatalyst ratio was controlled so that the Al:Zr molar ratio was 300:1. Abimodal polymer was produced which was 797 g/10 min melt index. Thedensity was 0.9678 g/cc. A residual zirconium of 0.7 ppmw was calculatedbased on a reactor mass balance. SEC analysis and deconvolution using 4floury distributions was completed and the results are shown in Table I.

Example 3

[0210] An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 80° C. and 320 psig(2.2 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 53 pounds per hour(24 kg/hr), hexene was fed to the reactor at a rate of about 0.5 poundsper hour (0.22 kg/hr) and hydrogen was fed to the reactor at a rate of 9mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partialpressure in the reactor. The production rate was about 25 PPH. Thereactor was equipped with a plenum having about 990 PPH of recycle gasflow. (The plenum is a device used to create a particle lean zone in afluidized bed gas-phase reactor.) A tapered catalyst injection nozzlehaving a 0.055 inch (0.12) hole size was positioned in the plenum gasflow. A solution of 1 wt % Catalyst B in hexane catalyst was mixed with0.2 lb/hr (0.09 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube for about 15 minutes. The Catalyst B and hexenemixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a linefor about 20-25 minutes. In a separate activating stainless steel tube,a 1 wt % Catalyst A in toluene solution was activated with cocatalyst(MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes. The twoindependently activated solutions were combined into a single processline for about 4 minutes. The quantity of Catalyst A catalyst was about40-45 mol % of the total solution fed. In addition to the solution,isopentane and nitrogen were added to control particle size. The totalsystem was passed through the injection nozzle into the fluidized bed.MMAO to catalyst ratio was controlled so that the Al:Zr molar ratio was300:1. A bimodal polymer was produced which was 0.045 g/10 min meltindex and 7.48 g/10 min flow index. The density was 0.9496 g/cc. Aresidual zirconium of 1.7 ppmw was calculated based on a reactor massbalance. SEC analysis and deconvolution using 7-8 floury distributionswas completed and the results are shown in Table I.

Example 4

[0211] An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 320 psig(2.2 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 50 pounds per hour(22.7 kg/hr), some of the hexene was fed to the reactor at a rate ofabout 0.7 pounds per hour (0.32 kg/hr) and hydrogen was fed to thereactor at a rate of 11 mPPH. Ethylene was fed to maintain 220 psi (1.52MPa) ethylene partial pressure in the reactor. The production rate wasabout 29 PPH. The reactor was equipped with a plenum having about 970PPH of recycle gas flow. (The plenum is a device used to create aparticle lean zone in a fluidized bed gas-phase reactor.) A taperedcatalyst injection nozzle having a 0.055 inch (0.14 cm) hole size waspositioned in the plenum gas flow. A solution of 1 wt % Catalyst B inhexane catalyst was mixed with 0.2 lb/hr (0.09 kg/hr) hexene in a{fraction (3/16)} inch (0.48 cm) stainless steel tube for about 15minutes. The Catalyst B and hexene mixture were mixed with cocatalyst(MMAO-3A, 1 wt % Aluminum) in a line for about 20-25 minutes. In aseparate activating stainless steel tube, a 1 wt % Catalyst A in toluenesolution was activated with cocatalyst (MMAO-3A, 1 wt % Aluminum) forabout 50-55 minutes. The two independantly activated solutions werecombined into a single process line for about 4 minutes. The quantity ofCatalyst A catalyst was about 40-45 mol % of the total solution fed. Inaddition to the solution, isopentane and nitrogen were added to controlparticle size. The total system was passed through the injection nozzleinto the fluidized bed. MMAO to catalyst was controlled so that theAl:Zr molar ratio was 300:1. A bimodal polymer was produced which was0.054 g/10 min melt index and 7.94 g/10 min flow index. The density was0.948 g/cc. A residual zirconium of 1.1 ppmw was calculated based on areactor mass balance. SEC analysis and deconvolution using 7-8 flourydistributions was completed and the results are shown in Table I.

Example 5

[0212] An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 320 psig(2.2 MPa) total reactor pressure having a water cooled heat exchangerEthylene was fed to the reactor at a rate of about 60 pounds per hour(27.2 kg/hr), hexene was fed to the reactor at a rate of about 0.8pounds per hour (0.36 kg/hr) and hydrogen was fed to the reactor at arate of 13 mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa)ethylene partial pressure in the reactor. The production rate was about34 PPH. The reactor was equipped with a plenum having about 960 PPH ofrecycle gas flow. (The plenum is a device used to create a particle leanzone in a fluidized bed gas-phase reactor.) A tapered catalyst injectionnozzle having a 0.055 inch (0.14 cm) was positioned in the plenum gasflow. A solution of 1 wt % Catalyst B in hexane catalyst was mixed with0.2 lb/hr (0.09 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube for about 15 minutes. The Catalyst B and hexenemixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a linefor about 20-25 minutes. In a separate activating stainless steel tube,a 1 wt % Catalyst A in toluene solution was activated with cocatalyst(MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes. The twoindependently activated solutions were combined into a single processline for about 4 minutes. The quantity of Catalyst A catalyst was about40-45 mol% of the total solution fed. In addition to the solution,isopentane and nitrogen were added to control particle size. The totalsystem was passed through the injection nozzle into the fluidized bed.MMAO to catalyst ratio was controlled so that the Al:Zr molar ratio was300:1. A bimodal polymer was produced which was 0.077 g/10 min meltindex and 12.7 g/10 min flow index. The density was 0.9487 g/cc. Aresidual zirconium of 0.9 ppmw was calculated based on a reactor massbalance. SEC analysis and deconvolution using 7-8 floury distributionswas completed and the results are shown in Table I.

Example 6

[0213] An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 320 psig(2.2 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 60 pounds per hour(27.2 kg/hr), hexene was fed to the reactor at a rate of about 0.8pounds per hour (0.36 kg/hr) and hydrogen was fed to the reactor at arate of 13 mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa)ethylene partial pressure in the reactor. The production rate was about34 PPH. The reactor was equipped with a plenum having about 1,100 PPH ofrecycle gas flow. (The plenum is a device used to create a particle leanzone in a fluidized bed gas-phase reactor.) A tapered catalyst injectionnozzle having a 0.055 inch (0.14 cm) was positioned in the plenum gasflow. A solution of 1 wt % Catalyst B in hexane catalyst was mixed with0.2 lb/hr (0.09 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube for about 15 minutes. The Catalyst B and hexenemixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a linefor about 10-15 minutes. 1 wt % Catalyst A in toluene solution was addedto the activated Catalyst B solution for about 5 minutes before beingsprayed into the reactor. The quantity of Catalyst A catalyst was about40-45 mol % of the total solution fed. In addition to the solution,isopentane and nitrogen were added to control particle size. The totalsystem was passed through the injection nozzle into the fluidized bed.MMAO to catalyst ratio was controlled so that the final Al:Zr molarratio was 300:1. A bimodal polymer was produced which was 0.136 g/10 minmelt index and 38.1 g/10 min flow index. The density was 0.9488 g/cc. Aresidual zirconium of 0.5 ppmw was calculated based on a reactor massbalance. SEC analysis and deconvolution using 7-8 floury distributionswas completed and the results are shown in Table I.

Example 7

[0214] An ethylene-hexene copolymer was produced in a 14-inch (35.6cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 42 pounds per hour(19.1 kg/hr), hexene was fed to the reactor at a rate of about 0.8pounds per hour (0.36 kg/hr) and hydrogen was fed to the reactor at arate of 13 mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa)ethylene partial pressure in the reactor. The production rate was about32 PPH. The reactor was equipped with a plenum having about 2010 PPH ofrecycle gas flow. (The plenum is a device used to create a particle leanzone in a fluidized bed gas-phase reactor.) A tapered catalyst injectionnozzle having a 0.055 inch (0.14 cm) was positioned in the plenum gasflow. A solution of 0.25 wt % Catalyst B in hexane catalyst was mixedwith 0.1 lb/hr (0.05 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube. The Catalyst B and hexene mixture were mixed withcocatalyst (MMAO-3A, 1 wt % Aluminum) in a line for about 15 minutes.0.5 wt % Catalyst A in toluene solution was added to the activatedCatalyst B solution for about 15 minutes before being sprayed into thereactor. The quantity of Catalyst A catalyst was about 65-70 mol % ofthe total solution fed. In addition to the solution, isopentane andnitrogen were added to control particle size. The total system waspassed through the injection nozzle into the fluidized bed. MMAO tocatalyst ratio was controlled so that the final Al:Zr molar ratio was500. A bimodal polymer was produced which was 0.06 g/10 min melt indexand 6.26 g/10 min flow index. The density was 0.9501 g/cc. A residualzirconium of 0.65 ppmw was calculated based on a reactor mass balance.SEC analysis and deconvolution using 7-8 floury distributions wascompleted and the results are shown in Table I. TABLE I Example 1 (Comp)2 (Comp) 3 4 5 6 7 I₂₁ (dg/min) 0.28 n/a 7.5 7.94 12.6 38.1 6.26 I₂₁/I₂— — 165.3 147 164.6 280.4 104 I₂ (dg/min) no flow 797 0.045 0.054 0.0770.136 0.060 Experimental SEC Data Mn 80,600 2,952 7,908 10,896 10,77810,282 8,700 Mw 407,375 13,398 340,011 263,839 259,389 261,138 287,961Mw/Mn 5.05 4.54 43 24.2 24.1 25.4 33.10 Mn (calculated) — — 7,645 10,55210,673 10,105 8,523 Mw (calculated) — — 339,752 258,282 248,215 252,310284,814 Mw/Mn (calculated) — — 44.44 24.48 23.26 24.97 33.42 LMW Mn —2,988 3,741 5,548 5,731 6,382 4,165 (calculated) LMW Mw (calc.) — 13,21413,259 16,388 15,214 18,333 11,771 LMW Mw/Mn — 4.42 3.54 2.95 2.65 2.872.83 (calc.) HMW Mn 73,979 — 122,758 111,256 85,461 88,374 115,954(calculated) HMW Mw (calc.) 407,513 — 633,154 501,013 484,657 607,625526,630 HMW Mw/Mn 5.51 — 5.16 4.50 5.67 6.88 4.54 (calc.) SPLIT(HMW/Total) 100.00 0.00 52.67 49.92 49.64 39.70 53.03 Reactor ConditionsReactor Temp (° C.) 85 80 80 85 85 85 85 C₂ psi/MPa 220/1.52 180/1.24220/1.52 220/1.52 220/1.52 220/1.52 220/1.52 H₂/C₂ mole ratio 0.00160.0018 0.0013 0.0014 0.0014 0.0010 0.0019 C₆/C₂ mole ratio 0.004880.00153 0.0074 0.0073 0.0077 0.0075 0.0050 Residence time (hr) 3.6 7.55.3 4.74 3.87 3.87 3.4 Molar ratio — — 0.71 0.73 0.76 0.76 2.16 HMW/LMWMolar % Catalyst A 100 — 41 42 43 43 68 Zr ppm, by lab — — 1.33 1.611.33 0.8 0.97 Zr ppm, by feed 1.63 — 1.46 1.06 0.9 0.54 0.62 Average1.63 — 1.40 1.34 1.12 0.67 0.80 Al/Zr mole ratio 400 — 330 380 320 307500 Catalyst B activity g — — 9,965 12,515 18,754 37,288 50,142 PE/mmolcat-hr Catalyst A activity g 15,559 — 15,730 17,042 24,323 32,465 26,203PE/mmol cat-hr

[0215] Comparative Examples 1 and 2 give experimental data on how thesingle component catalyst system behave. Examples 3 and 4 demonstratethe effect of temperature on essentially the same reactor conditions andcatalyst feed system. Note that at higher temperature, the M_(w)/M_(n)is lower, as is the MFR. Examples 5 and 6 compare the effect ofactivation scheme for essentially the same reactor conditions andcatalyst feed system. Note that in Example 6, the overall activity ofthe catalyst is better. However, the amount of high molecular weightmaterial produced is lower. Examples 6 and 7 demonstrate the ability tocontrol the amount of high molecular weight material produced atessentially similar reactor conditions. Example 7 fed a higherpercentage of Catalyst A feed, hence a higher quantity of higher Mwmaterial was produced.

Example 8

[0216] 350 pounds (159 kg) of polyethylene produced according to example4 above (referred to as Polymer A) was compounded on a Wemer-FleidererZSK-30 twin screw extruder with 1000 ppm Irganox™ 1076 and 1500 ppmIrgafos™ 1068 at a melt temperature of 220° C. and formed into pellets.Then the pellets were blown into a 0.5 mil (13 μm) film on an Alpineblown film extrusion line. The extrusion condition were: die-160 mmtriplex, 1.5 mm die gap, 400° C. die temperature, 48 inches (122 cm)layflat width, target melt temperature-410° F. (210° C.), and extrusionrates-310 lb/hr (144 kg/hr), 420 lb/hr (191 kg/hr) and 460 lb/hr (209kg/hr). ESCORENE™ HD7755.10 (a conventional series reactor product ofExxon Chemical Company, Houston, Tex.) was run at the same conditions asa comparison. All films were conditioned according to 23° C., 50%humidity for 40 hours. The data are reported in Table A. TABLE A PolymerA HD7755.10 Polymer A HD7755.10 Polymer A HD7755.10 Rate lb/hr/ 317(144) 317 (144) 421 (191) 421 (191) 460 (209) 460 (209) (kg/hr) FilmGage 0.524 mil/ 0.502 mil/ 0.532 mil/ 0.519 mil/ 0.543 mil/ 0.528 mil/13 μm 13 μm 14 μm 13 μm 14 μm 13 μm Density g/cc 0.9489 0.949 0.95020.949 0.9468 0.9489 26″ (66 cm) 355 g 308 g 327 g 325 g nm nm dart @ 1day 26″ (66 cm) 351 g 308 g 314 g 344 g 301 g 360 g dart @ 7 days MDTear 22 (0.87) 16 (0.63) 25 (0.98) 15 (0.59) 22 (0.87) 15 (0.59) g/mil(g/μ) TD Tear 97 (3.82) 102 (4.02) 77 (3.03) 84 (3.31) 100 (3.94) 81(3.19) g/mil (g/μ) 1% Secant 161,000 200,200 159,000 183,800 156,200178,700 MD, psi (MPa) (1110) (1380) (1096) (1267) (1077) (1232) 1%Secant 184.500 212,500 163,500 206,600 161,400 212,500 TD, psi (MPa)(1272) (1465) (1127) (1425) (1113) (1465) MD UT Str. 14445 14347 1257415110 12934 15609 psi (MPa) (100) (99) (87) (104) (89) (108) TD UT Str.13369 12124 10785 12278 11727 11482 psi (MPa) (92) (84) (74) (85) (81)(79) U Elong. % 285 293 246 296 253 299 U. Elon. % 317 393 305 377 340377 Haze % 59.6 64.0 57.8 62.0 56.9 60.9 45° Gloss 13.6 10.8 13.4 12.014.9 11.9

[0217] ESCORENE HD7755.10 is a polyethylene polymer available from ExxonChemical Company, Houston, Tex., having an I₂₁ of 7.5, and MIR of 125,an M_(w) of 180,000, a density of 0.95 g/cc, produced using a dualreactor system.

Example 9

[0218] Several drums of granular samples (produced following thepolymerization procedure above with a molar catalyst ratio (CatalystA/Catlayst B) of 2.3 were tumble mixed with 1000 ppm Irganox™ 1076 and1500 ppm Irgafos™ 1068 and 1500 ppm of calcium stearate. Thistumble-mixed granluar resin was pelletized on a 2½″ (6.35 cm) Prodexcompounding line at 400° F. (204° C.). Thus prepared pellets were filmextruded on a 50 mm Alpine blown film line which is equipped with anextruder with 50 mm single screw (18:1 L/D ratio) and 100 mm annular diewith 1 mm die gap. The extrusion conditions were: 400° F. (204° C.) dietemperature, output rate-100 lb/hr (46 kg/hr). A typical set temperatureprofile was: 380° F./400° F./400° F./400° F./400° F./400° F./410° F.(193° C./204° C./204° C./204° C./204° C./204° C./210° C./210° C.) forBarrel1/Barel2/Block adaptor/Bottom adaptor/Verical adaptor/Diebottom/Die middle/Die top. The pellet samples were extruded to produce1.0 mil (25 μm) film sample at the line speed of 92 fpm (48 cm/sec) and0.5 mil (13 μm) film sample at the line speed of 184 fpm (94 cm/sec) atthe blow-up ratio (BUR) of 4.0. For both cases the bubble showedexcellent stability with a typical “necked-in” wine glass shape. The FLH(frost line height) of blown bubble was maintained at 36 inches (91.4cm) and 40 inches (101.6 cm), respectively for 1.0 mil (25 μm) and 0.5mil (12.5 μm) film. The extrusion head pressure and motor load exhibitedslightly higher than ESCORENE™ HD7755.10 (a conventional series reactorproduct of Exxon Chemical Company in Mt Belvue Tex.) at the sameextrusion conditions. The resultant film properties are reported inTable B. All the film samples were conditioned at to 23° C., 50%humidity for 40 hours. Dart impact strength of 0.5 mil (12.5 μm) filmexhibited 380 g, which exceeded that of ESCORENE™ HD7755.10 which showed330 g. TABLE B Escorene ™ 7755 Polymer B I₂ (g/10 min) 0.08 0.062 I₂₁(g/10 min) 10 10.02 I₂₁/I₂ 134 160.5 Density (g/cc) 0.952 0.9485 Output(lb/hr) (kg/hr)   104 (47)  100 (47) Die rate (lb/hr/in die) ˜8 ˜8 Headpressure psi/MPa 7,200 (50) 7600 (53) Motor Load (amp) 56 61 BUR 4 4 FLH(inch) (cm)  36 (91.4)  40 (101.6)  36 (91.4)  40 (101.6) melt fractureno no no Bubble Stability good good good Take-up (fpm) (m/s)  92 (0.5) 185 (0.9)   92 (0.5)  184 (0.9) Film gauge (mil) (μ)    1 (25)   0.5(12.5)   1 (25)  0.5 (12.5) Dart Impact strength (g) 250 330 290 360Tensile str. (psi) (MPa) MD 8,400 (58) 11,300 (78) 8100 (56) 11400 (79)TD 7,900 (55) 10,400 (72) 7230 (50)  9520 (66) Elongation (%) MD 350 230410 330 TD 570 390 580 410 Elmendorf Tear (g/mil) (g/μ) MD  25 (0.98) 22 (0.87)  24 (0.95)   33 (1.30) TD 142 (5.59)  72 (2.83) 205 (8.07)  171 (2.80) Modulus (psi) (MPa) MD 127,000 (876)  144,000 (993) 131500(907)  135350 (933) TD 146,000 (1007)  169,000 (1165) 160250 (1105) 156300 (1078)

Example 10

[0219] Following the procedure of Example 9, several drums of granularsamples (Polymer C produced following the polymerization procedure abovewith a molar catalyst ratio of Catalyst A to Catalyst B of 0.732 andPolymer D produced following the polymerization procedure above with amolar catalyst ratio of Catalyst A to Catalyst B of 2.6) were tumblemixed with 1000 ppm Irganox™ 1076, 1500 ppm of calcium stearate and 1500ppm Irgafos™ 1068 then pelletized and extruded as described in Example9. All films were conditioned at 23° C. and 50% humidity for 40 hours.Dart impact strength of a 0.5 mil (12.5 um) film from both Polymer C andPolymer D exhibited 380 g, which exceeded that of ESCORENE™ HD 7755.10which showed 330 g. The data are reported in Table C. TABLE C SamplePolymer C Polymer D Escorene 7755 Rxn Temp (° C.) 85 85 C₂ (psi) (kPa)220 (1517) 220 (1517) H₂/C₂ (molar) 0.0014-0.0016 0.00102 C₆/C₂ (molar)0.0075-0.0078 0.00531-0.00586 Mn 14,600 16,400 Mw 309,100 298,200291,500 Mw/Mn 21.2 18.2 15.7 HMW/LMW 53.8/46.2 50.5/49.5 I₂ (g/10 min)0.056 0.049 0.08 I₂₁ (g/10 min) 6.48 6.7 10 MFR (I₂₁/I₂) 115.8 138 134Density (g/cc) 0.9487 0.9461 0.952 Output (lb/hr) (kg/hr) 102 (46) 102(46) 100 (45) Die rate (lb/hr/in die) ˜8 ˜8 10 Head. (psi) (MPa) 8,120(56) 7,890 (54) 7,230 (50) Motor Load (amp) 64.5 63 59 BUR 4 4 4 FLH(inch) (cm) 40 (101.6) 40 (101.6) 36 (91.4) 40 (101.6) 36 (91.4) 40(101.6) melt fracture no no no Bubble Stability Fair Good Good Good GoodGood Film gauge (mil) (μm) 1 (25.4) 0.5 (12.7) 1 (25.4) 0.5 (12.7) 1(25.4) 0.5 (12.7) Dart Impact (g) 200 380 200 380 250 330 Tensilestrength MD (psi) (MPa) 10,300 19,900 9,900 15,500 8,400 11,300 (71)(137) (68) (107) (58) (78) TD (psi) (MPa) 7,900 13,800 8,400 14,5007,900 10,400 (55) (95) (58) (100) (55) (72) Elongation (%) MD 320 240290 250 350 230 TD 630 385 610 350 570 390 Elmendorf Tear MD (g/mil)(g/μm) 24 (0.95) 21 (0.83) 36 (1.42) 36 (1.42) 25 (0.98) 22 (0.87) TD(g/mil) (g/μm) 410 (16.1) 87 (3.4) 350 (13.8) 66 (2.6) 142 (5.6) 72(2.8) Modulus MD (kpsi) (MPa) 105 (724) 120 (827) 103 (710) 110 (758)127 (876) 144 (993) TD (psi) (MPa) 128 (883) 126 (869) 129 (889) 114(786) 146 169 (1007) (1165)

[0220] In addition to the examples above, other variations onpolymerizing using the catalyst systems described herein include:

[0221] 1. Compound I could be dissolved in a solvent, preferably tolueneto form the desired weight % solution then used in combination withother catalyst systems.

[0222] 2. Catalyst A could be used as a 0.50 weight % solution intoluene and Catalyst B could be used as a 0.25 weight % solution inhexane at molar ratios of B to A of about 0.7 when the two are activatedseparately then mixed together (parallel activation) or at molar ratiosof B to A of 2.2 to 1.5 when A is activated then B is added (sequentialactivation).

[0223] 3. Raising or lowering the reaction temperature to narrow orbroaden the Mw/Mn, respectively.

[0224] 4. Changing residence time to affect product properties. Largechanges can have significant impact. One to five, preferably four hoursresidence time appears to produce good product properties.

[0225] 5. Spraying the catalyst into the reactor in such a way as tocreate a particle lean zone. A particle lean zone can be created by a50,000 lb/hr flow of cycle gas through 6 inch pipe. The catalyst can beatomized w/a spray nozzel using nitrogen atomizing gas.

[0226] 6. The activator, preferably MMAO 3A can be used at 7 weight % alin isopentane, hexane or heptane at feed rate sufficient to give anAl/Zr ratio of 100 to 300.

[0227] 7. Catalyst A is mixed on-line with MMAO 3A then Catalyst B isadded on line, then the mixture is introduced into the reactor.

[0228] 8. Catalyst A is mixed on-line with MMAO 3A and Catalyst B ismixed on line with MMAO 3A thereafter the two activated catalysts aremixed on-line then introduced into the reactor.

[0229] All documents described herein are incorporated by referenceherein, including any priority documents and/or testing procedures. Asis apparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. It is within the scope of thisinvention to use two or more Group 15 containing metal compounds withone or more bulky ligand metallocene-type catalyst system and/or one ormore conventional type catalyst system. Accordingly it is not intendedthat the invention be limited thereby.

We claim:
 1. A continuous gas phase polymerization process comprisingcombining in a single gas phase reactor olefin monomers with a catalystcomposition comprising an activator, a first catalyst compoundcomprising a Group 15-containing metal compound and a second catalystcompound; wherein the Group 15-containing metal compound is representedby the formula:

wherein M is a Group 4 metal, each X is independently a leaving group, nis the oxidation state of M, m is the formal charge of the ligandcomprising Y, Z and L, L is a Group 15 element, Y is a Group 15 element,Z is a Group 15 element, R¹ and R² are independently a C₁ to C₂₀hydrocarbon group, or a heteroatom containing group having up to twentycarbon atoms, the heteroatom selected from the group consisting ofsilicon, germanium, tin, lead, and phosphorus; wherein optionally, R¹and R² are interconnected to each other, and/or R⁴ and R⁵ may beinterconnected to each other, R³ is absent, a hydrocarbon group, ahydrogen, a halogen, or a heteroatom containing group, R⁴ and R⁵ areindependently an alkyl group, an aryl group, a substituted aryl group, acyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkylgroup, a substituted cyclic arylalkyl group or a multiple ring system,and R⁶ and R⁷ are independently absent, hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group; wherein a polyolefin isproduced; and wherein the melt index (I₂) of the polyolefin is changedby altering the amount of the second catalyst component.
 2. The processof claim 1, wherein the second catalyst system comprises a bulky ligandmetallocene compound, a Ziegler-Natta catalyst, a Phillips-typecatalyst, a vanadium catalyst, or combinations thereof; wherein theZiegler-Natta catalyst comprises MR_(x), where M is a metal from Group 4to 6, and R is a halogen or a hydrocarbyloxy group, and x is theoxidation state of the metal M; wherein the Phillips-type catalystcomprises CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, or chromium acetylacetonate (Cr(AcAc)₃); andwherein the vanadium catalyst comprises vanadyl trihalide, alkoxyhalides and alkoxides, vanadium tetra-halide and vanadium alkoxyhalides, vanadium or vanadyl acetyl acetonates.
 3. The process of claim1, wherein R⁴ and R⁵ are represented by the formula:

wherein R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, or a heteroatom containing groupcontaining up to 40 carbon atoms wherein any two R⁸⁻¹² groups may form acyclic group or a heterocyclic group.
 4. The process of claim 1, whereinthe second catalyst compound comprises a bulky ligand metallocenecompound of the general formula L^(D)MQ₂(YZ)X_(n) wherein M is a Group4, 5 or 6 metal atom, L^(D) is a cyclopentadienyl ligand that is bondedto M, Q₂(YZ) forms a unicharged polydentate ligand, wherein Q isselected from the group consisting of —O—, —NR—, —CR₂— and —S—; Y is C;Z is selected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃,—PR₂, —H, and substituted or unsubstituted aryl groups, with the provisothat when Q is —NR— then Z is selected from one of the group consistingof —OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is a hydrocarbon groupcontaining from 1 to 20 carbon atoms; X is a univalent anionic group ora divalent anionic group, and n is 1 or
 2. 5. The process of claim 1,wherein the second catalyst compound comprises a bulky ligandmetallocene compound of the general formula: L ^(A) L ^(B) MQ _(n) or L^(A) AL ^(B) MQ _(n) wherein M is a Group 4, 5 or 6 metal atom; L^(A)and L^(B) are selected from the group consisting of cyclopentadienyl,tetrahydroindenyl, indenyl, fluorenyl, and substituted versions thereof;Q is a monoanionic leaving group; A is a divalent bridging groupcontaining at least one Group 13 to Group 16 atom; and n is 0, 1 or 2.6. The process of claim 3, wherein R⁹, R¹⁰ and R¹² are independently amethyl, ethyl, propyl or butyl group.
 7. The process of claim 3, whereinR⁹, R¹⁰ and R¹² are methyl groups, and R⁸ and R¹¹ are hydrogen.
 8. Theprocess of claim 1, wherein M is a Group 4 metal, L, Y, and Z areindependently nitrogen, R¹ and R² are a hydrocarbon radical, R³ ishydrogen, and R⁶ and R⁷ are absent.
 9. The process of claim 4, wherein Mis a Group 4 metal and L^(D) is an indenyl group or a fluorenyl group.10. The process of claim 1, wherein the Group 15-containing metalcompound to the second catalyst system are present in a molar ratio of20:80 to 80:20.
 11. The process of claim 1, wherein the activator isselected from the group consisting of an alumoxane, a modifiedalumoxane, non-coordinating ionic activators, non-coordinating neutralactivators, and combinations thereof.
 12. The process of claim 1,wherein the process is conducted at a temperature of from 30° C. to 120°C.
 13. The process of claim 1, wherein the olefins consist of ethyleneand at least one comonomer having from 4 to 8 carbon atoms.
 14. Theprocess of claim 1, wherein hydrogen from 100 ppm to 5000 ppm is alsocombined.
 15. The process of claim 1, wherein the catalyst compositionis introduced into the reactor in a solvent.
 16. The process of claim 1,wherein the catalyst composition also comprises a support.
 17. Theprocess of claim 13, wherein the process is capable of producing apolyethylene copolymer having a Mw/Mn between 20 and 60, and a densityof between 0.94 to 0.97 g/cm³; wherein the ethylene is copolymerizedwith 1-butene or 1-hexene; wherein the second catalyst compound is abulky ligand metallocene catalyst component and the activator is analumoxane, the Al/Zr molar ratio ranging from 300:1 to 100:1, and themolar ratios of the metals from the first and second catalyst compoundsranges from 30:70 to 70:30.
 18. The process of claim 13, wherein theprocess is capable of producing a polyethylene copolymer having aresidual metal content of 5.0 ppm transition metal or less; wherein theethylene is copolymerized with 1-butene or 1-hexene; wherein the secondcatalyst compound is a bulky ligand metallocene catalyst component. 19.The process of claim 17 or 18, wherein the polyethylene copolymer isformed into a pipe having a notch tensile test value of greater than 500hrs at 3.0 MPa as measured under ASTM F1473.